CN108801992B - Fe3+Molecular fluorescence sensor and preparation method thereof - Google Patents

Fe3+Molecular fluorescence sensor and preparation method thereof Download PDF

Info

Publication number
CN108801992B
CN108801992B CN201810381408.6A CN201810381408A CN108801992B CN 108801992 B CN108801992 B CN 108801992B CN 201810381408 A CN201810381408 A CN 201810381408A CN 108801992 B CN108801992 B CN 108801992B
Authority
CN
China
Prior art keywords
compound
preparation
solvent
molecular fluorescence
mixed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810381408.6A
Other languages
Chinese (zh)
Other versions
CN108801992A (en
Inventor
戴宇
赵建永
张文昕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Shoutong Technology Development Co ltd
Institute of Biophysics of CAS
Original Assignee
Suzhou Shoutong Technology Development Co ltd
Institute of Biophysics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Shoutong Technology Development Co ltd, Institute of Biophysics of CAS filed Critical Suzhou Shoutong Technology Development Co ltd
Priority to CN201810381408.6A priority Critical patent/CN108801992B/en
Publication of CN108801992A publication Critical patent/CN108801992A/en
Application granted granted Critical
Publication of CN108801992B publication Critical patent/CN108801992B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices

Abstract

The present invention provides a kind of Fe3+Molecular fluorescence sensor and preparation method thereof.The Fe3+Molecular fluorescence sensor includes test layer, and test layer includes the first gel base and the Fe that is scattered in the first gel base3+Molecular fluorescence compound, Fe3+Molecular fluorescence compound has structure shown in Formulas I, and in Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.By this Fe3+Molecular fluorescence compound is dispersed in the test layer in the first gel base as sensor, so that Fe provided by the invention3+Molecular fluorescence sensor Fe in measurement sample3+Have many advantages, such as when concentration measurement efficiency height, high sensitivity, accuracy it is good, it is reversible measurement and reproducibility it is high.

Description

Fe3+Molecular fluorescence sensor and preparation method thereof
Technical field
The present invention relates to organic syntheses and element analysis technology field, in particular to a kind of Fe3+Molecular fluorescence sensing Device and preparation method thereof.
Background technique
Iron is one of internal the most abundant microelement, it is the important of composition hemoglobin, myoglobins and a variety of enzymes Ingredient takes part in the processes such as oxygen intake, oxygen metabolism, electronics transfer.If lacking iron in vivo, the synthesis of hemoglobin can be influenced, Can make the activity of the enzymes such as cytochrome c, ribonucleotide reductase, succinate dehydrogenase reduces, so as to cause serious body Dysfunction.Fe in human body3+The change of content is related to many diseases, as iron deficiency will lead to anaemia, cancer, diabetes and organ Dysfunction etc., and Fe supply then can by Fenton's reaction generate Cells Induced by Reactive Oxygen Species Alzheimer's disease, Huntington's disease and Parkinson's disease etc..Therefore, the content of iron ion in environment and human body is quick and precisely detected for the strong of Environmental security and the mankind Health has a very important significance.
Currently, detection micro Fe3+Analytical technology there are many kinds of, including atomic absorption spectrography (AAS), plasma emissioning light Spectrum, plasma mass, electrochemical process, titration etc..These methods are needed mostly using expensive large-scale instrument, and operation is multiple It is miscellaneous, portability difference and unsuitable on line real-time monitoring.The equipment as needed for fluorescence analysis is simple, and have fast response time, High sensitivity, it is easy to operate the advantages that, therefore using fluorescence probe come qualitative and quantitative detect Fe3+Have become research hotspot.
In recent years, about Fe3+The existing a small amount of report of the research of fluorescence probe.Wherein most is using rhodamine as fluorescent base The iron ion fluorescence probe of group, such as Chinese patent CN107011351A, CN 105884788A, Synthesis and evaluation of a novel rhodamine B-based'off-on'fluorescent chemosensor for the selective determination of Fe3+Ions, Sensors and Actuators B:Chemicals, 2017,242,921-931.The testing principle of rhodamine fluorescence probe are as follows: by causing acyl in itself with Action of Metal Ions Open loop occurs for amine Spirocyclic structure, and so as to cause ultravioletvisible absorption and fluorescence spectrum to change, it is different to be finally reached detection The purpose of concentration of metal ions.
However, structure will be broken from above-mentioned principle it is found that rhodamine fluorophor once carries out test reaction It is bad.Therefore, rhodamine is not fixed type dye, it is impossible to be used in reversible measurement.Further, since rhodamine can participate in ion coupling instead It answers, therefore its excitation wavelength and launch wavelength can change because detecting the variation of ion, lead to the rhodamine of a variety of different ions Base fluorescent optical sensor cannot be detected with the same excitation and launch wavelength.And the Fe of above-mentioned report3+Fluorescent optical sensor swashs Wavelength about 560nm is sent out, transmitted wave is about 580nm, and Stokes (Stockes) displacement only has 20nm or so, normal light credit Light microscopic piece is difficult to an exciting light and fluorescence distinguishes, so that testing result is influenced, the general spectrum high using spectral resolution Detection device carries out fluorescence signal acquisition, and detection difficulty and cost can greatly increase.
Based on the above reasons, it is not involved in ionic reaction using one kind, the bigger fluorophor of Stokes shift carries out Fe3+ Molecular fluorescence sensor design be very it is necessary to.
Summary of the invention
The main purpose of the present invention is to provide a kind of Fe3+Molecular fluorescence sensor and preparation method thereof, it is existing to solve Fe in technology3+Molecular fluorescence sensor reversible can not measure, and the problem that accuracy is inadequate.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of Fe3+Molecular fluorescence sensor, Including test layer, test layer includes the first gel base and the Fe that is scattered in the first gel base3+Molecular fluorescence compound, Fe3+Molecular fluorescence compound has structure shown in Formulas I:
In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.
Further, Polym is the residue of the residue of aminocellulose dehydrogenation formation, amino maltodextrin dehydrogenation formation Or the residue that amino polyvinylpyrrolidone dehydrogenation is formed；It is preferred that aminocellulose is amino ethyl cellulose, amino ethoxy One of cellulose, amino hydroxypropyl cellulose and aminocarbonyloxymethyl cellulose are a variety of.
Further, Fe3+Molecular fluorescence sensor includes: transparent resin basal layer；Test layer is arranged in transparent resin matrix On one side surface of bottom；Light shield layer is arranged on the surface of separate transparent resin basal layer side of test layer.
Further, light shield layer includes the second gel base and the opacifying fillers that are dispersed in the second gel base；It is preferred that Opacifying fillers are carbon black.
Further, the first gel base and the second gel base are respectively selected from D4 hydrogel, D6 hydrogel, acryloyl Amine-one of acrylonitrile copolymer and polyvinyl alcohol is a variety of.
Further, the material of transparent resin basal layer is one of PET, PMMA, PC, PVC, PS, PP and ABS or more Kind.
According to another aspect of the present invention, a kind of Fe is additionally provided3+The preparation method of molecular fluorescence sensor comprising with Lower step:
Compound A and compound B is carried out condensation reaction, forms compound C by step S1；Compound A, compound B and change The structure for closing object C is as follows, and wherein the X in compound A is halogen:
Compound C is hydrolyzed reaction and obtains compound D by step S2；The structure of compound D is as follows:
Compound D and amidized large hydrophilic molecular polymer are carried out condensation amidation process, obtained by step S3 Fe3+Molecular fluorescence compound；
Step S4, by Fe3+Molecular fluorescence compound is dispersed in the first gel base and is formed test layer, and then obtains Fe3+Molecular fluorescence sensor.
Further, amidized large hydrophilic molecular polymer is aminocellulose, amino maltodextrin or amino Polyvinylpyrrolidone；Preferably, before step S1, preparation method further includes the steps that prepare compound A comprising: it will 4- cyanobenzoic acid and the tert-butyl alcohol carry out esterification, obtain the 4- cyanobenzoic acid tert-butyl ester；By the tertiary fourth of 4- cyanobenzoic acid Ester, catalyst and methanol are mixed to form mixed system, and hydrogen is passed through into mixed system and carries out hydrogenation, obtains 4- amino first Yl benzoic acid tert-butyl ester E；Wherein catalyst is one of Raney nickel, palladium-carbon catalyst and Co catalysts or a variety of；By 4- Aminomethyl benzoic acid tert-butyl ester E is reacted with compound F, obtains compound A；The wherein 4- aminomethyl benzoic acid tert-butyl ester E, compound F has the following structure:
Wherein the X in compound F is halogen.
Further, step S1 includes: to mix compound A, compound B and acid binding agent with the first solvent, obtains first Mixture；First mixture is subjected to condensation reaction at a temperature of 80~100 DEG C, obtains the first product system；By the first product System is cooled and poured into water, and precipitating, as compound C is obtained by filtration；Preferably, the first solvent be N-Methyl pyrrolidone, One of N, N- dimethyl acetamide, dimethyl sulfoxide, dimethyl acetamide and tetrahydrofuran are a variety of；Preferably, acid is tied up Agent is N, one of N- diisopropylethylamine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine or a variety of； Preferably, the molar ratio between compound A, compound B and acid binding agent is 1~6:1~5:1~15；Preferably, in filtration step Later, step S1 further includes the steps that washing precipitating, and washing step includes: that precipitating is dissolved in chloroform, to Water is wherein added to be washed, liquid separation obtains organic phase and water phase；Using the dry organic phase of anhydrous sodium sulfate, filters and evaporates, Obtain compound C.
Further, step S2 includes: that compound C, carbonyl removing reagent and the second solvent are mixed and reacted, and obtains the Two product systems；It uses volume ratio to dilute the second product system for the chloroform of 1:1/methanol mixed solution, then evaporates molten Agent obtains compound D；Preferably, carbonyl removing reagent is trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mix Reagent or silica gel；Preferably, the second solvent is methylene chloride and/or chloroform；Preferably, the molal quantity of compound C is de- for carbonyl Except the 1.8~2.0% of reagent molal quantity, preferably 1.9%.
Further, step S3 includes: by compound D, amidized large hydrophilic molecular polymer, dehydrating agent, carbonyl Activator is mixed and is reacted with third solvent, obtains third product system；Third product system is filtered, and to filtering gained Precipitating is washed, is dried, and Fe is obtained3+Molecular fluorescence compound；Preferably, the carbonization of dehydrating agent N, N- dicyclohexyl -1,3- Diimine, 1- (3- dimethylamino-propyl) one of -3- ethyl-carbodiimide hydrochloride and diisopropylcarbodiimide or more Kind；Preferably, carbonyl activation agent is n-hydroxysuccinimide and/or N- hydroxy thiosuccinimide；Preferably, third is molten Agent is N, N- dimethylformamide, N, one in N- diethylformamide, DMAC N,N' dimethyl acetamide and hexamethylphosphoramide Kind is a variety of；Preferably, the dosage of compound D is the 2~3% of the weight of amidized large hydrophilic molecular polymer；It is preferred that Ground, before by amidized large hydrophilic molecular mixed with polymers, step S3 further include: by amidized large hydrophilic molecular Polymer is suspended in aqueous sodium carbonate, and filtering is resuspended in DMF, is filtered, then washed with DMF, is obtained pretreated ammonia The large hydrophilic molecular polymer of base.
Further, the step of 4- cyanobenzoic acid and the tert-butyl alcohol being subjected to esterification include: by 4- cyanobenzoic acid, The 4th solvent of acylating reagent is mixed and is reacted, and obtains intermediary；After removing the solvent in intermediary, by it with esterification catalyst, The tert-butyl alcohol is mixed and is reacted, and obtains the 4th product system；The 4th product system is purified, the 4- cyanobenzoic acid tert-butyl ester is obtained；It is excellent Selection of land, acylating reagent are one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；Preferably, esterification is urged Agent is one of pyridine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine or a variety of；Preferably, 4- cyanogen Molar ratio between yl benzoic acid and acylating reagent is 2~3:3~5；Volume ratio between esterification catalyst and the tert-butyl alcohol is 1~ 1.1:1。
Further, in the step of preparing 4- aminomethyl benzoic acid tert-butyl ester E, the 4- cyanobenzoic acid tert-butyl ester and catalysis Weight ratio between agent is 10~20:1~3；Weight ratio between the 4- cyanobenzoic acid tert-butyl ester and methanol is 1~3:8~20； Preferably, after being passed through hydrogen, the pressure of reaction system is 0.8~1.2MPa.
Further, the step of 4- aminomethyl benzoic acid tert-butyl ester E being reacted with compound F includes: by 4- ammonia Ylmethyl t-butyl perbenzoate E, compound F are mixed and are reacted with the 5th solvent, obtain the 5th product system；Filter the 5th product Obtained precipitating is dried system, obtains compound A；Preferably, the 5th solvent is ethyl alcohol, methanol, propyl alcohol and isopropanol One of or it is a variety of；Preferably, the molar ratio between 4- aminomethyl benzoic acid tert-butyl ester E and compound F is 1:1.
Further, step S4 includes: step S41, provides transparent resin basal layer；Step S42, by Fe3+Molecular fluorescence Compound, the gel rubber material of the first gel base and the mixing of the first gel solvent, are coated on transparent resin for obtained mixture On one side surface of basal layer, test layer is formed after dry；Step S43, by opacifying fillers, the gel rubber material of the second gel base And second gel solvent mixing, obtained mixture is coated on to a side surface of the separate transparent resin basal layer of test layer, Light shield layer is formed after drying, and then obtains Fe3+Molecular fluorescence sensor；Preferably, the first gel solvent and the second gel solvent It is the mixed solvent of water and ethyl alcohol.
The present invention provides a kind of Fe3+Molecular fluorescence sensor, the Fe3+Molecular fluorescence sensor includes test layer, test Layer includes the first gel base and the Fe being dispersed in first gel base3+Molecular fluorescence compound.Above-mentioned Fe3+Molecule is glimmering Optical compounds, for fluorophor, make it have good photostability with 1,8- naphthalene Asia amide, excite (449nm) and transmitting light (521nm) is wavelength visible, and Stokes shift is big (72nm), and quantum yield is high.Meanwhile the Fe3+Molecular fluorescence It closes in objectGroup (test group) is for Fe3+Sensitivity it is higher, pyridine nuclear nitrogen and 4- bit amino nitrogen energy Enough and Fe3+Complexing occurs and forms ion complexation body, so as to cause electronics transfer or energy transfer, makes the compound in difference Fe3+There is different fluorescence responses under concentration.Moreover, because the chelation structure has invertibity, so that provided by the invention Fe3+Molecular fluorescence compound, that is, corresponding sensor has good reversible test performance, and its reproducibility is preferable.Except this with Outside, the Fe3+Amidized large hydrophilic molecular polymeric groups in molecular fluorescence compound can play to fluorophor and The fixed function and good peptizaiton for testing group enable fluorophor and test group to better disperse and come, and Amidized large hydrophilic molecular polymeric groups itself provides micropore, make the Fe in sample to be tested3+It can be more fully Into and with test group more sufficiently faster contact so that Fe provided by the invention3+Molecular fluorescence compound has both Better test accuracy and sensitivity.By this Fe3+Molecular fluorescence compound is dispersed in the first gel base as sensing The test layer of device, so that Fe provided by the invention3+Molecular fluorescence sensor Fe in measurement sample3+There is measurement effect when concentration The advantages that rate height, high sensitivity, accuracy be good, reversible measurement and reproducibility are high.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows Fe according to the present invention3+The structural schematic diagram of molecular fluorescence sensor；
Fig. 2 shows the tert-butyl -4- amine picoline -1,8- naphthalimides that the embodiment of the present invention 1 is prepared The hydrogen nuclear magnetic resonance spectrogram of ylmethyl；
Fig. 3 shows the 4- amine picoline -1,8- naphthalimido methylbenzene that the embodiment of the present invention 1 is prepared The hydrogen nuclear magnetic resonance spectrogram of formic acid；
Fig. 4 shows Fe obtained in the embodiment of the present invention 13+Fluorescent optical sensor is with Fe3+Concentration increases fluorescence spectrum Variation diagram；
Fig. 5 shows Fe obtained in the embodiment of the present invention 13+Fluorescent optical sensor is with Fe3+Concentration increases fluorescence intensity Variation diagram；
Fig. 6 shows Fe obtained in the embodiment of the present invention 13+Fluorescent optical sensor is to Fe3+Fluorescence selectivity identify signal Figure；
Fig. 7 shows Fe made from the embodiment of the present invention 13+Fluorescent optical sensor detects Fe3+Anti-interference identify signal Figure；
Fig. 8 shows Fe made from the embodiment of the present invention 13+Fluorescent optical sensor is to various concentration Fe3+Dynamic response.
Wherein, the above drawings include the following reference numerals:
10, transparent resin basal layer；20, test layer；30, light shield layer.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally Apply for range claimed.
As described in background technology part, Fe in the prior art3+Molecular fluorescence sensor reversible can not measure, and Test accuracy is inadequate.
To solve the above-mentioned problems, the present invention provides a kind of Fe3+Molecular fluorescence sensor, as shown in Figure 1, the Fe3+Point Sub- fluorescent optical sensor includes test layer 20, and test layer 20 includes the first gel base and the Fe being scattered in the first gel base3+ Molecular fluorescence compound, Fe3+Molecular fluorescence compound has structure shown in Formulas I:
In Formulas I, Polym is amidized large hydrophilic molecular polymeric groups.
Above-mentioned Fe provided by the invention3+Molecular fluorescence sensor includes test layer, test layer include the first gel base and The Fe being dispersed in first gel base3+Molecular fluorescence compound.Above-mentioned Fe3+Molecular fluorescence compound is with 1,8- naphthalene Asia acyl Amine is fluorophor, makes it have good photostability, and exciting (449nm) and transmitting light (521nm) is that long wavelength is visible Light, Stokes shift is big (72nm), and quantum yield is high.Meanwhile the Fe3+In molecular fluorescence compoundGroup (is surveyed Try group) for Fe3+Sensitivity it is higher, pyridine nuclear nitrogen and 4- bit amino nitrogen can be with Fe3+Complexing occurs to be formed Ion complexation body makes the compound in different Fe so as to cause electronics transfer or energy transfer3+There is difference under concentration Fluorescence response.Moreover, because the chelation structure has invertibity, so that Fe provided by the invention3+Molecular fluorescence compound is Corresponding sensor has good reversible test performance, and its reproducibility is preferable.In addition to this, the Fe3+Molecular fluorescence chemical combination Amidized large hydrophilic molecular polymeric groups in object can play to fluorophor and test group fixed function and Good peptizaiton enables fluorophor and test group to better disperse and come, and amidized large hydrophilic molecular Polymeric groups itself provides micropore, make the Fe in sample to be tested3+It more fully can more be filled into and with test group Divide faster contact, so that Fe provided by the invention3+Molecular fluorescence compound has had both better test accuracy and spirit Sensitivity.By this Fe3+Molecular fluorescence compound is dispersed in the test layer in the first gel base as sensor, so that of the invention The Fe of offer3+Molecular fluorescence sensor Fe in measurement sample3+There is measurement efficiency height, high sensitivity, accuracy when concentration The advantages that good, reversible measurement and high reproducibility.
To sum up, either in aqueous solution or in human body fluid, Fe provided by the invention3+Molecular fluorescence sensor The Fe in measurement sample3+Have that measurement efficiency height, high sensitivity, accuracy are good, reversible measure and reproducibility height etc. is excellent when concentration Point illustrates good analytical characteristics, to Fe3+Concentration linear response range be 4~1000 μm of ol/L, Monitoring lower-cut is 1.42μmol/L。
It should be noted that in the above-mentioned Formulas I of the present invention(here referred to as functional group) and Molar ratio between Polym large hydrophilic molecular polymeric groups is not defined as 1:1, large hydrophilic molecular polymer matrix The load capacity of functional group is can be carried out according to the amido functional group quantity in corresponding large hydrophilic molecular polymer in group Adjustment, only indicate between functional group and large hydrophilic molecular polymeric groups to be connected by way of chemical bond herein.
In a preferred embodiment, above-mentioned Polym include but is not limited to aminocellulose dehydrogenation formed residue, The residue that the residue or amino polyvinylpyrrolidone dehydrogenation that amino maltodextrin dehydrogenation is formed are formed.These residues are actually The group formed after amidized large hydrophilic molecular polymer removes amino hydrogen atom.It is preferred that aminocellulose is amino second One of base cellulose, amino hydroxyethyl cellulose, amino hydroxypropyl cellulose and aminocarbonyloxymethyl cellulose are a variety of.This A little macro-radicals all have good hydrophily, and can be formed between above-mentioned functional group it is stable be connected chemically, and For above-mentioned functional group dispersion performance more preferably, the carrier as functional group can further increase Fe3+Molecular fluorescence Close stability, sensitivity and the measurement accuracy of object.Moreover, these macro-radicals and final Fe3+In molecular fluorescence sensor Basal layer between have good adhesive property, be also beneficial to further increase the stability of product.
In a preferred embodiment, as shown in Figure 1, Fe3+Molecular fluorescence sensor includes transparent resin basal layer 10, test layer 20 and light shield layer 30, test layer 20 are arranged on a side surface of transparent resin basal layer 10, and test layer 20 includes First gel base and the Fe being scattered in the first gel base3+Molecular fluorescence compound；Light shield layer 30 is arranged in test layer 20 Separate 10 side of transparent resin basal layer surface on.
In a preferred embodiment, light shield layer 30 includes the second gel base and is dispersed in the second gel base Opacifying fillers；It is preferred that opacifying fillers are carbon black.It can be improved the shading performance of light shield layer 30 using above-mentioned opacifying fillers, thus Advantageously reduce the interference for being further reduced light for fluorescence detection.In actually detected, the second gel base and shading are filled out Weight ratio between material can be adjusted according to detection environment, this is that those skilled in the art should be understood that.In order into One step reduces light interference, another aspect formula light shield layer have relatively high cohesive force suggest the second gel base of the invention and Weight ratio between opacifying fillers is 3.2:1.
In a preferred embodiment, the first gel base and the second gel base are respectively selected from D4 hydrogel, D6 One of hydrogel, nitrile-acrylamide-acrylic acid lonitrile copolymer and polyvinyl alcohol are a variety of.Above-mentioned Fe provided by the invention3+Molecule There is better compatibility, compound is more preferable in dispersibility wherein between fluorescent chemicals and these types of hydrogel.Except this with Outside, there is better adhesive property between these types of hydrogel and basal layer, be conducive to further increase Fe3+Molecular fluorescence sensing The stability of device.In addition, sensor of the invention is for testing micro Fe in liquid3+Content, Fe in test layer 203+Molecule Weight ratio between fluorescent chemicals and the first gel base can be according to micro Fe in prepare liquid3+Content be adjusted, this And those skilled in the art should be understood that.
In a preferred embodiment, the material of transparent resin basal layer 10 include but is not limited to PET, PMMA, PC, One of PVC, PS, PP and ABS or a variety of.The transparency that these types of resin material has more preferably, is conducive to further increase The Stability and veracity of fluorescence detection.
In a preferred embodiment, transparent resin basal layer 10 with a thickness of 75~125 μm, the thickness of test layer 20 Degree be 100~200 μm, light shield layer 30 with a thickness of 100~200 μm.
According to another aspect of the present invention, a kind of above-mentioned Fe is additionally provided3+The preparation method of molecular fluorescence sensor, packet Include following steps:
Compound A and compound B is carried out condensation reaction, forms compound C by step S1；Compound A, compound B and change The structure for closing object C is as follows, and wherein the X in compound A is halogen:
Compound C is hydrolyzed reaction and obtains compound D by step S2；The structure of compound D is as follows:
Compound D and amidized large hydrophilic molecular polymer are carried out condensation amidation process, obtained by step S3 Fe3+Molecular fluorescence compound；
Step S4, by Fe3+Molecular fluorescence compound is dispersed in the first gel base and is formed test layer, and then obtains Fe3+Molecular fluorescence sensor.
As it was noted above, either in aqueous solution or in human body fluid, utilizing Fe made from the preparation method3+Molecule Fluorescent optical sensor Fe in measurement sample3+There is good measurement efficiency height, high sensitivity, accuracy, reversible measurement and again when concentration The advantages that now property is high, illustrates good analytical characteristics, to Fe3+Concentration linear response range be 4~1000 μM, detection Lower limit is 1.42 μM.
At the same time, the present invention utilizes compound A and the condensation reaction of compound B, the hydrolysis of compound C, chemical combination Object D is reacted with amidized large hydrophilic molecular polymer, has synthesized above-mentioned Fe with shorter route3+Molecular fluorescence chemical combination Object, and the preparation method technological operation is simple, mild condition, is very suitable for industrializing large-scale application.
Preferably, above-mentioned amidized large hydrophilic molecular polymer is aminocellulose, amino maltodextrin or ammonia Base polyvinylpyrrolidone；More preferable aminocellulose is amino ethyl cellulose, amino hydroxyethyl cellulose, amino hydroxypropyl One of cellulose and aminocarbonyloxymethyl cellulose are a variety of.
Above compound A can select commercial product, in a preferred embodiment, before step S1, the system Preparation Method further includes the steps that prepare compound A comprising: 4- cyanobenzoic acid and the tert-butyl alcohol are subjected to esterification, obtained The 4- cyanobenzoic acid tert-butyl ester；By the 4- cyanobenzoic acid tert-butyl ester, catalyst (Raney nickel, palladium-carbon catalyst and Co catalysts One of or it is a variety of) and methanol be mixed to form mixed system, be passed through into mixed system hydrogen carry out hydrogenation, obtain 4- Aminomethyl benzoic acid tert-butyl ester E；4- aminomethyl benzoic acid tert-butyl ester E is reacted with compound F, obtains compound A； Wherein 4- aminomethyl benzoic acid tert-butyl ester E, compound F have the following structure:
Wherein the X in compound F is halogen.
Using above method prepare compound A, route is brief, simple process, cost is lower, yield is relatively high.
Concrete technology condition in above each synthesis step can be adjusted, specific as follows:
In a preferred embodiment, above-mentioned steps S1 includes: by compound A, compound B and acid binding agent and first Solvent mixing, obtains the first mixture；By the first mixture at 80~100 DEG C, more preferably carry out being condensed at a temperature of 90 DEG C anti- It answers, obtains the first product system；First product system is cooled and poured into water, precipitating, as compound C is obtained by filtration.
Preferably, the first solvent includes but is not limited to N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl Asia One of sulfone, dimethyl acetamide and tetrahydrofuran are a variety of.
Preferably, above-mentioned acid binding agent is N-Methyl pyrrolidone, n,N-dimethylacetamide, dimethyl sulfoxide, dimethyl One of acetamide and tetrahydrofuran are a variety of.Using these types of acid binding agent, be conducive to further increase compound A and chemical combination Reaction efficiency between object B improves reaction conversion ratio.
Preferably, the molar ratio between compound A, compound B and acid binding agent is 1~6:1~5:1~15；Preferably, exist After filtration step, step S1 further includes the steps that washing precipitating, and washing step includes: that precipitating is dissolved in three chloromethanes In alkane, water is added thereto and is washed, liquid separation obtains organic phase and water phase；Using the dry organic phase of anhydrous sodium sulfate, filtering And evaporate, obtain compound C.
It is exemplified below: by the chloro- 1,8- naphthalimide ylmethyl (compound A) of tert-butyl -4-, 2- amine first Yl pyridines (compound B) and n,N-diisopropylethylamine are suspended in N-Methyl pyrrolidone (NMP) and 18 small in 90 DEG C of heating When.Mixture is cooled and poured into water.Precipitating is obtained by filtration, is then dissolved in CHCl3In and be washed with water, liquid separation.Organic layer Use Na2SO4It dries, filters and evaporates, obtain crude product, 55~60 DEG C of hot methanol hot beating of crude product filters and with 0 ~10 DEG C of cold methanol washing.50~55 DEG C of hot CHCl of obtained solid (solid after cold methanol washing)3Recrystallization, obtains Yellow crystal tert-butyl -4- amine picoline -1,8- naphthalimide ylmethyl (compound C).
In a preferred embodiment, above-mentioned steps S2 includes: that compound C, carbonyl removing reagent and second is molten Agent is mixed and is reacted, and obtains the second product system；Use volume ratio for the chloroform of 1:1/methanol mixed solution dilution second Then product system evaporates solvent, obtain compound D.Using the tertbutyloxycarbonyl of carbonyl removing reagent elimination reaction object C (BOC) group.Volume ratio is used to can be used as solvent cut back for chloroform/methanol mixed solution of 1:1, to go Except excessive carbonyl removes reagent.
Preferably, above-mentioned carbonyl removing reagent is trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mixing try Agent or silica gel.For reducing side reaction and simplifying the purpose of aftertreatment technology, more preferably removed using trifluoroacetic acid as carbonyl Reagent.
Preferably, the second solvent is methylene chloride and/or chloroform, wherein smaller, more environmentally friendly using methylene chloride toxicity.It is excellent Selection of land, the molal quantity of compound C are that carbonyl removes the 1.8~2.0% of reagent molal quantity, more preferably 1.9%.
It is exemplified below: trifluoroacetic acid (TFA) is added to tert-butyl -4- amine picoline -1,8- naphthalimide base CH where methyl benzoic acid ester (compound C)2Cl2In solution.Acquired solution is stirred at room temperature about 1 hour, until thin layer color Spectrum detection (TLC) shows that most of tert-butyl -4- amine picoline -1,8- naphthalimido methyl benzoic acid ester disappears. Then by the mixture CHCl of volume ratio 1:13: MeOH dilutes and evaporates solvent.Repeat 4 to 8 times to remove TFA, then Being placed in pump is completely dried it in upper 30 minutes, obtains yellow crystal 4- amine picoline -1,8-naphthalimide ylmethyl benzene Formic acid (compound D).
In a preferred embodiment, above-mentioned steps S3 includes: by compound D, amidized large hydrophilic molecular Polymer, dehydrating agent, carbonyl activation agent are mixed and are reacted with third solvent, obtain third product system；Third is filtered to produce Objects system, and filtering gained precipitating is washed, is dried, obtain Fe3+Molecular fluorescence compound.It can using carbonyl activation agent The carbonyl in activating compounds D is improved, cooperation dehydrating agent is conducive to improve the conversion ratio of reaction.Preferably, dehydrating agent N, N- Dicyclohexyl -1,3- carbodiimides (DCC), 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDCI) and One of diisopropylcarbodiimide (DIC) is a variety of；Preferably, carbonyl activation agent is n-hydroxysuccinimide (NHS) And/or N- hydroxy thiosuccinimide (Sulfo-NHS).
Preferably, third solvent is n,N-Dimethylformamide (DMF), N, N- diethylformamide (DEF), N, N- diformazan One of yl acetamide (DMAC) and hexamethylphosphoramide (HMPT) are a variety of；Preferably, the dosage of compound D is amino 2~3% (more preferably the weight ratio of the two is 13:500) of the weight of the large hydrophilic molecular polymer of change；Preferably, it is inciting somebody to action Before amidized large hydrophilic molecular mixed with polymers, step S3 further include: by amidized large hydrophilic molecular polymer It is suspended in aqueous sodium carbonate, filters, be resuspended in DMF, filter, then washed with DMF, obtain pretreated amidized Large hydrophilic molecular polymer.Amidized large hydrophilic molecular polymer can be washed using the step, and is removed therein Moisture.
It is exemplified below: large hydrophilic molecular polymer (such as amino ethyl cellulose) is suspended in aqueous sodium carbonate 30min, filtering, is resuspended in DMF 30 minutes, filters, is washed twice with DMF, to replace the water of retention.It then will washing Large hydrophilic molecular polymer afterwards is transferred to (to be changed containing 4- amine picoline -1,8- naphthalimido methyl benzoic acid Close object D), N is mixed in the anhydrous DMF of N- dicyclohexyl -1,3- carbodiimides (DCC) and n-hydroxysuccinimide (NHS) It closes, and mixed suspension is stirred at room temperature 20 hours.Then crude product is obtained by filtration, with DMF, water, HCl, water, NaOH, water, acetone, ether washing are finally dried in vacuo 16h, obtain yellow powder, as the Fe3+Molecular fluorescence compound.
In a preferred embodiment, include: by 4- cyanobenzoic acid and the step of tert-butyl alcohol progress esterification 4- cyanobenzoic acid, acylating reagent and the 4th solvent are mixed and reacted, intermediary is obtained；After removing the solvent in intermediary, It is mixed and reacted with esterification catalyst, t-butanol mixture, the 4th product system is obtained；The 4th product system is purified, is obtained To the 4- cyanobenzoic acid tert-butyl ester.Acylation reaction first is carried out with 4- cyanobenzoic acid using acylating reagent and forms intermediate product, so It can react to form the 4- cyanobenzoic acid tert-butyl ester with the tert-butyl alcohol under the action of esterification catalyst afterwards.Compared to acid with it is pure straight It is reversed to answer, the 4- cyanobenzoic acid tert-butyl ester is prepared using the route provided by the invention, feed stock conversion is higher.Preferably, acyl Change reagent is one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；Preferably, esterification catalyst is Pyridine, N, one of N- dimethylformamide (DMF), 4-dimethylaminopyridine (DMAP) and triethylamine or a variety of.
Preferably, the molar ratio between 4- cyanobenzoic acid and acylating reagent is 2~3:3~5, more preferable 2:3；It will esterification The total weight of catalyst and the tert-butyl alcohol is denoted as n, the weight for removing the intermediary of solvent is denoted as m, m:n is 1~3:10~20, more Preferably 3:20；Volume ratio between esterification catalyst and the tert-butyl alcohol is 1~1.1:1, preferably 1:1.
It is exemplified below: 4- cyanobenzoic acid is dissolved in anhydrous CH2Cl2In, oxalyl chloride and dimethylformamide (DMF) is added. Gained mixture is stirred at room temperature 1 hour, until stopping generating gas.Remove solvent, gained residue pyridine/tertiary fourth Alcohol mixture is handled and is stirred at room temperature 6 hours.Solvent is evaporated under reduced pressure, and green residue is suspended in water, then uses Ethyl acetate extraction.Na is used after combined organic layer is washed2SO4It dries and evaporates.Crude product passes through ethyl acetate/petroleum ether After column purification, the white solid 4- cyanobenzoic acid tert-butyl ester is obtained.
In a preferred embodiment, in the step of preparing 4- aminomethyl benzoic acid tert-butyl ester E, 4- cyano benzene first Weight ratio between tert-butyl acrylate and catalyst is 10~20:1~3, more preferably 10:1；The 4- cyanobenzoic acid tert-butyl ester and first Weight ratio between alcohol is 1~3:8~20, more preferably 3:20；Preferably, after being passed through hydrogen, the pressure of reaction system is 0.8 ~1.2MPa, more preferable 1MPa.Using above-mentioned technique prepare 4- aminomethyl benzoic acid tert-butyl ester E, reaction it is more efficient, on One of Raney nickel, palladium-carbon catalyst and Co catalysts or a variety of can specifically be used by stating catalyst.
It is exemplified below: the 4- cyanobenzoic acid tert-butyl ester and Raney nickel is mixed in methyl alcohol, the hydrogen under the pressure of 1MPa Change 16 hours.Then solvent is removed under reduced pressure in Filtration of catalyst, obtain the white solid 4- aminomethyl benzoic acid tert-butyl ester.
In a preferred embodiment, step 4- aminomethyl benzoic acid tert-butyl ester E reacted with compound F Suddenly include: that 4- aminomethyl benzoic acid tert-butyl ester E, compound F are mixed and reacted with the 5th solvent, obtain the 5th product body System；The 5th product system is filtered, obtained precipitating is dried, obtains compound A.
Preferably, the 5th solvent is one of ethyl alcohol, methanol, propyl alcohol and isopropanol or a variety of；Preferably, 4- amino first Molar ratio between yl benzoic acid tert-butyl ester E and compound F is 1:1.
It is exemplified below: the chloro- 1,8- naphthalic anhydride of 4- and the 4- aminomethyl benzoic acid tert-butyl ester is put into ethyl alcohol and is formed Suspension.It is stirred at room temperature 16 hours.The precipitating being obtained by filtration, it is 8 hours dry at 50 DEG C, obtain white powder tert-butyl- The chloro- 1,8- naphthalimide ylmethyl of 4-.
In a preferred embodiment, step S4 includes: step S41, provides transparent resin basal layer；Step S42, By Fe3+Molecular fluorescence compound, the gel rubber material of the first gel base and the mixing of the first gel solvent, obtained mixture is applied Cloth forms test layer after dry on a side surface of transparent resin basal layer；Step S43, by opacifying fillers, the second gel base Obtained mixture, is coated on the separate transparent resin basal layer of test layer by the gel rubber material of material and the mixing of the second gel solvent A side surface, form light shield layer after dry, and then obtain Fe3+Molecular fluorescence sensor.Opacifying fillers are dispersed in second to coagulate It can be used as the top that light shield layer is covered on test layer in gum base materials, light can be reduced in this way for the interference of fluorescence detection, Further increase the accuracy of fluorometric investigation.
Preferably, the first gel solvent and the second gel solvent are the mixed solvent of water and ethyl alcohol.For example volume ratio is 8 ~10 ethanol/water mixed solvent.
In short, Fe provided by the invention3+Fluorescent optical sensor has the advantage that
(1) Fe in sensor3+Molecular fluorescence compound has good photostability, excites (449nm) and transmitting light The advantages that (521nm) is wavelength visible, and Stokes shift is big (72nm), and quantum yield is high；
(2) the sensor energy selective enumeration method Fe designed by the present invention3+Variation, strong antijamming capability, and synthesis side Method is simple, and testing cost is low, reusable；
(3) light shield layer of sensor can be used to the color pair of veiling glare or sample in preferably removal environment in the present invention The interference of sample detection, while can also be filtered isolation to the macromolecular insoluble matter in sample, only allows solubility in sample Substance is contacted with test layer, improves detection accuracy；
(4) preferably, the first hydrogel in the present invention and the second hydrogel can allow Fe3+Molecular fluorescence compound and screening It is dispersed in light uniform filling substrate surface, further increases the homogeneity of sensor and stability.Also, the hydrogel It can increase adhesiveness, test layer and light shield layer enable easily to be fixed together with basal layer very much, without UV solidification, heat cure etc. Process simplifies fixed process；
(5) Fe of the invention3+Fluorescent optical sensor both can satisfy larger range Fe3+The survey of concentration (4-1000 μm of ol/L) It is fixed, and may be implemented to Fe3+METHOD FOR CONTINUOUS DETERMINATION, substantially increase detection efficiency, high sensitivity, favorable reproducibility, long service life. Large hydrophilic molecular polymeric groups and the excellent isolation of light shield layer have also widened its application range, as the sensor can answer Used in fields such as biological electrolyte fluorescence analysis, medicament high flux screening and environmental monitorings, wherein uncured precursor substance is (such as Compound D) it can be used for the fields such as fluorescence probe, cell dyeing and fluorescence imaging.
Above-mentioned Fe3+The preparation method of molecular fluorescence sensor is relatively simple, it is only necessary in the table of transparent resin basal layer 10 The face last time is coated with test layer 20 and light shield layer 30.Such as:
By Fe3+Molecular fluorescence compound is mixed with D4 hydrogel solution (D4 hydrogel is dissolved in second alcohol and water), and At least 18h is stirred at room temperature, keeps it evenly dispersed in hydrogel.Then the suspension is uniformly coated on transparent tree with scraper On aliphatic radical bottom 10, at least dry 30min.With will equally be mixed and stirred for D4 hydrogel solution, at least carbon black of 18h is outstanding Supernatant liquid scraper is in Fe3+Continue even spread above fluorescent fiber element film, the uniform Fe of two layers of thickness can be obtained3+Fluorescence passes (upper layer is silica aerogel layer, lower layer Fe to sensor3+Fluorescent fiber element layer)
Beneficial effects of the present invention are further illustrated by the following examples:
Embodiment 1
The synthesis of compound 1
4- cyanobenzoic acid (80g, 544mmol) is dissolved in anhydrous CH2Cl2In (1000mL).Addition oxalyl chloride (104mL, 816mmol) and dimethylformamide (DMF) 10mL.Resulting reaction mixture is stirred at room temperature 1 hour, until stopping Generate gas.Remove solvent.Gained residue is handled with 600mL pyridine/t-butanol mixture (1:1) and is stirred at room temperature 6 Hour.Solvent is evaporated under reduced pressure, and green residue is suspended in H2In O.Aqueous suspension is extracted with ethyl acetate (3 × 500mL) It takes.By combined organic layer 10%KHSO4(2 × 500mL), H2O(500mL)NaHCO3(500mL), H2O (500mL) and salt Water (500mL) washing.By solvent Na2SO4It dries and evaporates.Crude product by using ethyl acetate/petroleum ether (1:4) column Chromatography purifying, obtains white solid 58g (yield 52%).
The synthesis of compound 2
The mixing in methanol (500mL) by the 4- cyanobenzoic acid tert-butyl ester (58g, 37mol) and Raney nickel (5.8g), in It is hydrogenated 16 hours under the pressure of 10kg.Then solvent is removed under reduced pressure in Filtration of catalyst, obtain white solid 47g (yield 80%).
The synthesis of compound 3
By the chloro- 1,8- naphthalic anhydride of 46.4g (200mmol) 4- and 41.4g (200mmol) 4- aminomethyl benzoic acid uncle Butyl ester, which is put into 250mLEtOH, forms suspension.It is stirred 16 hours at RT.The precipitating being obtained by filtration is small in 50 DEG C of dryings 8 When, obtain white powder 48g (yield 57%).
The synthesis of compound 4
By 24.33g (225mmol) 2- amine picoline and the chloro- 1,8- naphthalene diformazan of 31.3g (74.3mmol) tert-butyl -4- Imide methyl benzoic acid ester and 13mL (74.6mmol) n,N-diisopropylethylamine are suspended in 110mLN- methyl pyrrolidone (NMP) and at 90 DEG C it heats 18 hours.Mixture is cooled and poured into water (2L).Precipitating is obtained by filtration, is then dissolved in CHCl3It is washed in (800mL) and with water (5 × 800mL).Organic layer Na2SO4It dries, filters and evaporates, it is thick to obtain 63.55g Product.Residue is ground with hot methanol (600mL), filters and is washed with cold methanol (600mL).The hot CHCl of obtained solid3 Recrystallization, obtains yellow crystal 32.0g (yield 87%), tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl Benzoic ether, hydrogen nuclear magnetic resonance spectrogram are as shown in Figure 2.
The synthesis of compound 5
87.5mL (1.14mol) trifluoroacetic acid (TFA) is added to 10.68g (21.64mmol) tert-butyl -4- amine methyl Pyridine -1,8- naphthalimide ylmethyl is in CH2Cl2In the solution of (160mL).Acquired solution is stirred in room temperature It mixes about 1 hour, until thin-layer chromatography detection (TLC) shows most of tert-butyl -4- amine picoline -1,8- naphthalene diformazan imide Ylmethyl disappears.Then by the CHCl of mixture 1:13: MeOH (1.2L) dilutes and evaporates solvent.Repeat 6 Secondary to remove TFA, being subsequently placed in pump is completely dried it in upper 30 minutes, obtains yellow crystal 9.35g (yield 99%), 4- amine Picoline -1,8- naphthalimido methyl benzoic acid, hydrogen nuclear magnetic resonance spectrogram are as shown in Figure 3.
The synthesis of compound 6
Amino ethyl cellulose (5g) is suspended in 30min in 50mL2.5% aqueous sodium carbonate, filters, suspends again 30 minutes in 50mLDMF, filtering is washed twice with DMF, to replace the water of retention.Then the cellulose of washing is transferred to Containing 4- amine picoline -1,8- naphthalimido methyl benzoic acid (0.13g, 0.3mmol), N, dicyclohexyl -1 N-, 3- carbodiimides (DCC, 0.62g, 3mmol) and n-hydroxysuccinimide (NHS, 0.35g, 3mmol) are in anhydrous DMF It is mixed in the solution of (20mL), and mixed suspension is stirred at room temperature 20 hours.Then yellow fibers are obtained by filtration Cellulose fiber, with DMF (5 × 50mL), water (50mL), 0.2NHCl (2 × 50mL), water (50mL), 1.0NNaOH (2 × 50mL, 60 DEG C, 30min), water (10 × 50mL), acetone (2 × 50mL), ether (2 × 50mL) washing, be finally dried in vacuo 16h, obtain Huang Color powder 0.54g.
Fe3+The production of fluorescent optical sensor
The 4- amine picoline -1,8-naphthalimide ylmethyl-benzamide cellulose 0.3g for taking 25 μm of sieves, with D4 hydrogel solution 4.7mL (D4 hydrogel 0.47g is dissolved in 3.807mL ethyl alcohol and 0.309mL water) mixing, and at room temperature At least 18h is stirred, keeps it evenly dispersed in hydrogel.Then the suspension is uniformly coated on the poly- of 100 μ m-thicks with scraper On ester (PET) diaphragm (light transmittance is more than or equal to 88%), at least dry 30min.With will be with D4 hydrogel solution 4.85mL (D4 hydrogel 0.485g is dissolved in 3.929mL ethyl alcohol and 0.437mL water) is mixed and stirred for at least carbon black of 18h (0.15g) Suspension scraper is in Fe3+Continue even spread above fluorescent fiber element film, the uniform Fe of two layers of thickness can be obtained3+Fluorescence Sensor (upper layer is silica aerogel layer, with a thickness of 150 μm, lower layer Fe3+Fluorescent fiber element layer, with a thickness of 150 μm).
Fe3+The fluorescence property of fluorescent optical sensor is tested
(1)Fe3+Fluorescent optical sensor is to various concentration Fe3+Spectral signature
0.1622g iron chloride is dissolved in the Tris-HCl buffer of 0.05mol/L pH 6.0, it is fixed with 100mL volumetric flask Hold and is made 1.0 × 10-2The Fe of mol/L3+Stock solution continues with the buffer to Fe obtained3+Stock solution carry out repeatedly by Grade dilution, to obtain a series of difference Fe3+The titer of concentration: 4 μm of ol/L, 8 μm of ol/L, 10 μm of ol/L, 40 μ Mol/L, 80 μm of ol/L, 100 μm of ol/L, 400 μm of ol/L, 800 μm of ol/L, 1000 μm of ol/L and 10000 μm of ol/L.By Fe3+It is glimmering Diagonally position is fixed in fluorescence cuvette optical sensor, photomultiplier tube voltage be 700V, excitation wavelength and Launch wavelength be respectively under conditions of 449nm and 521nm with fluorescence spectrophotometer measurement its in a series of above-mentioned difference Fe3+ The variation of transmitting photocathode in concentration standard liquid.Fig. 4 is Fe produced by the present invention3+Fluorescent optical sensor is with Fe3+Concentration Increase the variation diagram of fluorescence spectrum, it can be seen that Fe3+Fluorescent optical sensor is in Fe3+In the presence of show strong fluorescence It is quenched.With Fe3+The increase of concentration, fluorescence intensity of the sensor at 521nm gradually decrease.Fig. 5 is produced by the present invention Fe3+Fluorescent optical sensor is with Fe3+Concentration increases the variation diagram of fluorescence intensity, can see from the figure and works as Fe3+Concentration is in 4 μm of ol/ When within the scope of L-1000 μm of ol/L, fluorescence intensity and Fe3+Concentration is in good linear relationship, and the linear equation of fitting can To Fe3+Carry out quantitative detection.Fe is calculated according to the ratio of the standard deviation of 3 times of 10 blank solutions and fit equation slope3+ The detection of concentration is limited to 1.42 μm of ol/L
(2)Fe3+Spectral signature of the fluorescent optical sensor to 17 kinds of other heavy metal ion
By 17 metal ion species salt [NaCl, KCl, CH3COOLi·2H2O、Al(NO3)3、CaCl2、MgCl2·6H2O、 ZnCl2、 FeSO4·7H2O、CoCl2·6H2O、MnCl2·4H2O、CrCl3·6H2O、BaCl2·2H2O、NiCl2·6H2O、 CuCl2·2H2O、 CdCl2·2.5H2O、Pb(NO3)2、HgCl2] accurate with the Tris-HCl buffer of 0.05mol/LpH6.0 It is configured to the stock solution that respective concentration is 10mmol/L, is then diluted to 17 kinds of ion standards that concentration is 1000 μm of ol/L Liquid is spare.Simultaneously also configure each metal ion respectively with Fe3+The titer coexisted, so that single metal ion in every kind of titer With Fe3+Concentration be 1000 μm of ol/L.Fluorescence selectivity experiment is as shown in figure 5, be the Na of 1000 μm of ol/L by concentration+、K+、Li+、Al3+、 Ca2+、Mg2+、Zn2+、Fe2+、Co2+、Mn2+、Cr3+、Ba2+、Ni2+、Cu2+、Cd2+、Pb2+、Hg2+And Fe3+Ion mark Quasi- liquid takes 2ml that oblique cutting is added respectively Fe3+In the cuvette of fluorescent optical sensor, after fluorescent stabilization, wave is used under 700V voltage Its variation for emitting photocathode of the excitation light detection of a length of 449nm.Fig. 6 is observed it is found that Fe3+Fluorescent optical sensor is to Fe3+ There is apparent response effect, and fluorescence intensity is reduced to minimum at 521nm, this illustrates the sensor to Fe3+Have very well Selectivity.Cu is added2+Afterwards, the fluorescence intensity of sensor also slightly reduces, but other equivalent metal ions are to optrode film fluorescence Emissive porwer does not influence substantially.In order to further study other common metal cations to Fe3+The interference effect of measurement, I Carried out competitive assay, i.e., will contain 1000 μm of ol/L Fe of other ions (concentration is 1000 μm of ol/L)3+Solution is added To containing Fe3+(result is as shown in Fig. 7 white histogram) is measured in the cuvette of fluorescent optical sensor.It can by competitive assay Know, in addition to Cu2+, other ions and Fe3+Fluorescent emission intensity when coexisting at 521nm is without significant changes.Therefore, it removes Cu2+, (different metal cation is with chloride, nitrate, sulfate or acetic acid for other common metal cations and anion The form of salt is added) Fe that will not interfere3+Measurement.And work as Cu2+Concentration when being reduced to 100 μm of ol/L, to 1000 μm of ol/L Fe3+Detection no longer interfere.Therefore, this sensor is substantially feasible for practical application.
(3)Fe3+The reproducibility and invertibity of fluorescent optical sensor
By Fe3+Fluorescent optical sensor is sequentially placed into the Tris-HCl plain buffer of pH6.0,100 μm of ol/L Fe3+、pH6.0 Tris-HCl plain buffer and 10000 μm of ol/LFe3+Solution in carry out fluorescent emission intensity time sweep, each Scanning 180 seconds is handled, persistently scanning 60 minutes, as a result as shown in Figure 8.As can be seen from FIG. 8, to 10 repetitions of plain buffer Measurement, to 100 μm of ol/L Fe3+With 10000 μm of ol/L Fe3+The relative deviation of the fluorescent value of each five replications of solution 2% hereinafter, this illustrates that the invertibity of the sensor and reproducibility are satisfactory.The response time of this sensor is also very short, μm ol/L Fe from 0 to 100003+Concentration has very quick dynamic response, therefore the Fe suitable for different application scene3+It is dense The on-line monitoring of degree.
Embodiment 2
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 1, adjust The dosage of whole oxalyl chloride, makes the molar ratio 2:3 of 4- cyanobenzoic acid and oxalyl chloride, and the volume ratio between pyridine and the tert-butyl alcohol is 1.1:1.The yield of final compound 1 is 49%.
Embodiment 3
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 1, adjust The dosage of whole oxalyl chloride makes the molar ratio 3:5 of 4- cyanobenzoic acid and oxalyl chloride.The yield of final compound 1 is 53%.
Embodiment 4
The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 1 Oxalyl chloride replaces with thionyl chloride, and adjusts its dosage and make the molar ratio 3:2 of 4- cyanobenzoic acid and thionyl chloride,.By pyrrole Pyridine replaces with 4-dimethylaminopyridine, and adjusts its dosage and make volume ratio between 4-dimethylaminopyridine and the tert-butyl alcohol 1.2:1, the yield of final compound 1 are 45%.
Embodiment 5
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 2, adjust The dosage of whole catalyst makes the weight ratio 20:3 between the 4- cyanobenzoic acid tert-butyl ester and Raney nickel, adjusts the use of methanol Amount, makes the weight ratio 1:8 between the 4- cyanobenzoic acid tert-butyl ester and methanol.The yield of compound 2 is 82%.
Embodiment 6
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 2, adjust The dosage of whole catalyst makes the weight ratio 20:3 between the 4- cyanobenzoic acid tert-butyl ester and Raney nickel, adjusts the use of methanol Amount, makes the weight ratio 3:20 between the 4- cyanobenzoic acid tert-butyl ester and methanol.The yield of compound 2 is 84%.
Embodiment 7
The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 2 Raney nickel replaces with palladium-carbon catalyst, and adjusts the dosage of catalyst, makes the 4- cyanobenzoic acid tert-butyl ester and palladium-carbon catalyst Between weight ratio be 15:1, adjust the dosage of methanol, make the weight ratio 1 between the 4- cyanobenzoic acid tert-butyl ester and methanol: 6.The yield of compound 2 is 74%.
Embodiment 8
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 4, adjust The dosage of whole 2- amine picoline and n,N-diisopropylethylamine makes the chloro- 1,8-naphthalimide ylmethyl of tert-butyl -4- Molar ratio between benzoic ether, 2- amine picoline and n,N-diisopropylethylamine is 1:1:1.The yield of compound 4 is 85%.
Embodiment 9
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 4, adjust The dosage of whole 2- amine picoline and n,N-diisopropylethylamine makes the chloro- 1,8-naphthalimide ylmethyl of tert-butyl -4- Molar ratio between benzoic ether, 2- amine picoline and n,N-diisopropylethylamine is 6:5:15.The yield of compound 4 is 82%.
Embodiment 10
The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 4 N,N-diisopropylethylamine replaces with triethylamine, and adjusts the dosage of 2- amine picoline and triethylamine, keeps tert-butyl -4- chloro- Molar ratio between 1,8- naphthalimide ylmethyl, 2- amine picoline and triethylamine is 8:5:5.Compound 4 yield is 73%.
Embodiment 11
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 5, adjust The dosage of whole trifluoroacetic acid makes tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl molal quantity It is the 1.8% of trifluoroacetic acid molal quantity.The yield of compound 5 is 97%.
Embodiment 12
The technique of each step the difference is that only with embodiment 1 in the embodiment: in the synthesis process of compound 5, adjust The dosage of whole trifluoroacetic acid makes tert-butyl -4- amine picoline -1,8-naphthalimide ylmethyl molal quantity It is the 2.0% of trifluoroacetic acid molal quantity.The yield of compound 5 is 98%.
Embodiment 13
The technique of each step the difference is that only with embodiment 1 in the embodiment:, will in the synthesis process of compound 5 Trifluoroacetic acid replaces with volume ratio and is the hydrochloric acid and ethyl acetate mix reagent of 1:2, and adjusts its dosage, tert-butyl -4- amine first The molal quantity of yl pyridines -1,8- naphthalimide ylmethyl is the 3.0% of the mix reagent molal quantity.Chemical combination The yield of object 5 is 75%.
As can be seen from the above embodiments, Fe provided by the invention3+Molecular fluorescence sensor Fe in measurement sample3+When concentration Have many advantages, such as measurement efficiency height, high sensitivity, accuracy it is good, it is reversible measurement and reproducibility it is high.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (25)

1. a kind of Fe3+Molecular fluorescence sensor, which is characterized in that the Fe3+Molecular fluorescence sensor includes test layer (20), institute State the Fe that test layer (20) includes the first gel base He is scattered in first gel base3+Molecular fluorescence compound, institute State Fe3+Molecular fluorescence compound has structure shown in Formulas I:
In the Formulas I, Polym is the residue that amino ethyl cellulose dehydrogenation is formed.
2. Fe according to claim 13+Molecular fluorescence sensor, which is characterized in that the Fe3+Molecular fluorescence sensor packet It includes:
Transparent resin basal layer (10)；
The test layer (20) is arranged on a side surface of the transparent resin basal layer (10)；
Light shield layer (30) is arranged on the surface far from transparent resin basal layer (10) side of the test layer (20).
3. Fe according to claim 23+Molecular fluorescence sensor, which is characterized in that the light shield layer (30) includes second Gel base and the opacifying fillers being dispersed in second gel base.
4. Fe according to claim 33+Molecular fluorescence sensor, which is characterized in that the opacifying fillers are carbon black.
5. Fe according to claim 33+Molecular fluorescence sensor, which is characterized in that first gel base and described Second gel base is respectively selected from one of D4 hydrogel, D6 hydrogel, nitrile-acrylamide-acrylic acid lonitrile copolymer and polyvinyl alcohol Or it is a variety of.
6. the Fe according to any one of claim 2 to 53+Molecular fluorescence sensor, which is characterized in that the transparent resin The material of basal layer (10) is one of PET, PMMA, PC, PVC, PS, PP and ABS or a variety of.
7. a kind of Fe described in any one of claims 1 to 63+The preparation method of molecular fluorescence sensor, which is characterized in that institute State preparation method the following steps are included:
Compound A and compound B is carried out condensation reaction, forms compound C by step S1；The compound A, the compound B And the structure of the compound C is as follows, wherein the X in the compound A is halogen:
The compound C is hydrolyzed reaction and obtains compound D by step S2；The structure of the compound D is as follows:
The compound D and amino ethyl cellulose are carried out condensation amidation process, obtain Fe by step S33+Molecular fluorescence Close object；
Step S4, by the Fe3+Molecular fluorescence compound is dispersed in the first gel base and is formed test layer, and then obtains institute State Fe3+Molecular fluorescence sensor.
8. preparation method according to claim 7, which is characterized in that before the step S1, the preparation method is also Include the steps that preparing the compound A comprising:
4- cyanobenzoic acid and the tert-butyl alcohol are subjected to esterification, obtain the 4- cyanobenzoic acid tert-butyl ester；
The 4- cyanobenzoic acid tert-butyl ester, catalyst and methanol are mixed to form mixed system, led in Xiang Suoshu mixed system Enter hydrogen and carry out hydrogenation, obtains 4- aminomethyl benzoic acid tert-butyl ester E；Wherein the catalyst is Raney nickel, palladium carbon One of catalyst and Co catalysts are a variety of；
The 4- aminomethyl benzoic acid tert-butyl ester E is reacted with compound F, obtains the compound A；The wherein 4- Aminomethyl benzoic acid tert-butyl ester E, the compound F have the following structure:
Wherein the X in the compound F is halogen.
9. preparation method according to claim 7 or 8, which is characterized in that the step S1 includes:
The compound A, the compound B and acid binding agent are mixed with the first solvent, obtain the first mixture；
First mixture is subjected to the condensation reaction at a temperature of 80~100 DEG C, obtains the first product system；
First product system is cooled and poured into water, precipitating is obtained by filtration, the as described compound C.
10. preparation method according to claim 9, which is characterized in that
First solvent is one in N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide and tetrahydrofuran Kind is a variety of；
The acid binding agent is N, in N- diisopropylethylamine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine It is one or more；
Molar ratio between the compound A, the compound B and the acid binding agent is 1~6:1~5:1~15.
11. preparation method according to claim 9, which is characterized in that after filtration step, the step S1 further includes The step of washing to the precipitating, the washing step include:
The precipitating is dissolved in chloroform, water is added thereto and is washed, liquid separation obtains organic phase and water phase；
Using the dry organic phase of anhydrous sodium sulfate, filters and evaporate, obtain the compound C.
12. preparation method according to claim 7 or 8, which is characterized in that the step S2 includes:
The compound C, carbonyl removing reagent and the second solvent are mixed and reacted, the second product system is obtained；
It uses volume ratio to dilute second product system for the chloroform of 1:1/methanol mixed solution, then evaporates solvent, Obtain the compound D.
13. preparation method according to claim 12, which is characterized in that
Carbonyl removing reagent is trifluoroacetic acid, the hydrochloric acid that volume ratio is 1:2 and ethyl acetate mix reagent or silica gel；
Second solvent is methylene chloride and/or chloroform；
The molal quantity of the compound C is that the carbonyl removes the 1.8~2.0% of reagent molal quantity.
14. preparation method according to claim 13, which is characterized in that the molal quantity of the compound C is the carbonyl Remove the 1.9% of reagent molal quantity.
15. preparation method according to claim 7 or 8, which is characterized in that the step S3 includes:
The compound D, the amino ethyl cellulose, dehydrating agent, carbonyl activation agent are mixed with third solvent and carried out anti- It answers, obtains third product system；
The third product system is filtered, and filtering gained precipitating is washed, is dried, obtains the Fe3+Molecular fluorescence Close object.
16. preparation method according to claim 15, which is characterized in that
The dehydrating agent is N, N- dicyclohexyl -1,3- carbodiimides, 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide One of hydrochloride and diisopropylcarbodiimide are a variety of；
The carbonyl activation agent is n-hydroxysuccinimide and/or N- hydroxy thiosuccinimide；
The third solvent is N,N-dimethylformamide, N, N- diethylformamide, DMAC N,N' dimethyl acetamide and hexamethyl One of phosphoric triamide is a variety of；
The dosage of the compound D is the 2~3% of the weight of the amino ethyl cellulose.
17. preparation method according to claim 15, which is characterized in that the amino ethyl cellulose is being mixed it Before, the step S3 further include: the amino ethyl cellulose is suspended in aqueous sodium carbonate, filters, is resuspended in DMF In, filtering, then washed with DMF, obtain the pretreated amidized large hydrophilic molecular polymer.
18. preparation method according to claim 8, which is characterized in that by the 4- cyanobenzoic acid and the tert-butyl alcohol Carry out esterification the step of include:
The 4- cyanobenzoic acid, acylating reagent and the 4th solvent are mixed and reacted, intermediary is obtained；
After removing the solvent in the intermediary, it is mixed and reacted with esterification catalyst, the tert-butyl alcohol, the 4th product body is obtained System；
The 4th product system is purified, the 4- cyanobenzoic acid tert-butyl ester is obtained.
19. preparation method according to claim 18, which is characterized in that
The acylating reagent is one of oxalyl chloride, thionyl chloride, phosphorus trichloride and phosphorus pentachloride or a variety of；
The esterification catalyst is one of pyridine, N,N-dimethylformamide, 4-dimethylaminopyridine and triethylamine or more Kind；
Molar ratio between the 4- cyanobenzoic acid and the acylating reagent is 2~3:3~5；The esterification catalyst and institute Stating the volume ratio between the tert-butyl alcohol is 1~1.1:1.
20. the preparation method according to claim 8 or 18, which is characterized in that prepare the 4- aminomethyl benzoic acid uncle In the step of butyl ester E, the weight ratio between the 4- cyanobenzoic acid tert-butyl ester and the catalyst is 10~20:1~3；Institute Stating the weight ratio between the 4- cyanobenzoic acid tert-butyl ester and the methanol is 1~3:8~20.
21. preparation method according to claim 20, which is characterized in that after being passed through the hydrogen, the pressure of reaction system For 0.8~1.2MPa.
22. the preparation method according to claim 8 or 18, which is characterized in that by the tertiary fourth of 4- aminomethyl benzoic acid The step of ester E is reacted with the compound F include:
The 4- aminomethyl benzoic acid tert-butyl ester E, the compound F are mixed and reacted with the 5th solvent, the 5th production is obtained Objects system；
The 5th product system is filtered, obtained precipitating is dried, obtains the compound A.
23. preparation method according to claim 22, which is characterized in that
5th solvent is one of ethyl alcohol, methanol, propyl alcohol and isopropanol or a variety of；
Molar ratio between the 4- aminomethyl benzoic acid tert-butyl ester E and the compound F is 1:1.
24. preparation method according to claim 7, which is characterized in that the step S4 includes:
Step S41 provides transparent resin basal layer；
Step S42, by the Fe3+Molecular fluorescence compound, the gel rubber material of first gel base and the first gel solvent Mixing, obtained mixture is coated on a side surface of the transparent resin basal layer, forms test layer after dry；
Step S43 mixes opacifying fillers, the gel rubber material of the second gel base and the second gel solvent, the mixing that will be obtained Object is coated on the side surface far from the transparent resin basal layer of the test layer, light shield layer is formed after dry, and then obtain To the Fe3+Molecular fluorescence sensor.
25. preparation method according to claim 24, which is characterized in that first gel solvent and second gel Solvent is the mixed solvent of water and ethyl alcohol.
CN201810381408.6A 2018-04-25 2018-04-25 Fe3+Molecular fluorescence sensor and preparation method thereof Active CN108801992B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810381408.6A CN108801992B (en) 2018-04-25 2018-04-25 Fe3+Molecular fluorescence sensor and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810381408.6A CN108801992B (en) 2018-04-25 2018-04-25 Fe3+Molecular fluorescence sensor and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108801992A CN108801992A (en) 2018-11-13
CN108801992B true CN108801992B (en) 2019-08-02

Family

ID=64093019

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810381408.6A Active CN108801992B (en) 2018-04-25 2018-04-25 Fe3+Molecular fluorescence sensor and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108801992B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1634893A (en) * 2004-11-03 2005-07-06 大连理工大学 4,5-disubstituted-1,8-naphthoyl imide compounds and use thereof
WO2007074461A1 (en) * 2005-12-29 2007-07-05 Technion Research And Development Foundation Ltd. Method for detecting alkylating agents
CN101786985A (en) * 2010-02-05 2010-07-28 苏州大学 Naphthalimide derivative and use thereof as fluorescent probe
CN102234506A (en) * 2010-04-23 2011-11-09 华东理工大学 Purpose of 1,8-naphthalimide derivatives
CN105884788A (en) * 2016-05-13 2016-08-24 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B and preparation method and application of Fe<3+> molecular fluorescence sensor
CN106008343A (en) * 2016-06-23 2016-10-12 徐州工程学院 Naphthalimide based mercury-ion fluorescence probe as well as preparation method and application thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634689A (en) * 1985-10-31 1987-01-06 Schering Corporation Phosphinylalkanoyl imino acids
US8097725B2 (en) * 2004-12-03 2012-01-17 Roche Diagnostics Operations, Inc. Luminescent indicator dye and optical sensor
US9360474B2 (en) * 2012-11-29 2016-06-07 Opti Medical Systems, Inc. Multi-layer device for selectively determining magnesium ion
CN103408440B (en) * 2013-08-20 2014-12-10 天津希恩思生化科技有限公司 Organic compound for detecting content of metal ions in water environment
CN103772318B (en) * 2014-01-22 2015-11-11 天津希恩思生化科技有限公司 A kind of organic compound for measuring metal ion content in water surrounding and application thereof
CN104292204B (en) * 2014-09-05 2016-03-16 苏州福来兹检测科技有限公司 A kind of compound for measuring metal ion content in water surrounding and application thereof
CN104341347B (en) * 2014-10-21 2018-02-23 苏州福来兹检测科技有限公司 A kind of organic compound and its application for being used to prepare wide pH value fluorescence probe
DE102016103750B4 (en) * 2015-12-23 2018-04-05 Endress+Hauser Conducta Gmbh+Co. Kg Sensor cap for an optochemical sensor and corresponding optochemical sensor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1634893A (en) * 2004-11-03 2005-07-06 大连理工大学 4,5-disubstituted-1,8-naphthoyl imide compounds and use thereof
WO2007074461A1 (en) * 2005-12-29 2007-07-05 Technion Research And Development Foundation Ltd. Method for detecting alkylating agents
CN101786985A (en) * 2010-02-05 2010-07-28 苏州大学 Naphthalimide derivative and use thereof as fluorescent probe
CN102234506A (en) * 2010-04-23 2011-11-09 华东理工大学 Purpose of 1,8-naphthalimide derivatives
CN105884788A (en) * 2016-05-13 2016-08-24 南京理工大学 Fe<3+> molecular fluorescence sensor based on Rhodamine B and preparation method and application of Fe<3+> molecular fluorescence sensor
CN106008343A (en) * 2016-06-23 2016-10-12 徐州工程学院 Naphthalimide based mercury-ion fluorescence probe as well as preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Synthesis and photophysical properties of a novel green fluorescent polymer for Fe3+ sensing;Hu yulin 等;《Polymer International》;20081016;第57卷;第1343-1350页 *
萘酰亚胺衍生物的合成及对铁离子的识别;杜斌 等;《光谱学与光谱分析》;20150228;第35卷(第2期);第470-473页 *
萘酰亚胺衍生物荧光探针的研究进展;滕明爽 等;《染料与染色》;20130228;第50卷(第1期);第14-16页 *

Also Published As

Publication number Publication date
CN108801992A (en) 2018-11-13

Similar Documents

Publication Publication Date Title
CN109060733B (en) Iron ion molecular fluorescence sensor and preparation method thereof
Li et al. New lanthanide ternary complex system in electrospun nanofibers: Assembly, physico-chemical property and sensor application
Wang et al. Preparation of fluorescent nanofibrous film as a sensing material and adsorbent for Cu2+ in aqueous solution via copolymerization and electrospinning
CN105884788B (en) A kind of Fe3+ molecular fluorescences sensor based on rhodamine B, preparation method and application
Li et al. A triphenylamine-isophorone-based “off–on” fluorescent and colorimetric probe for Cu2+
CN105924449A (en) Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions
CN112209871B (en) Zinc ion fluorescent probe based on tetraphenylethylene and preparation method and application thereof
CN110240683A (en) A kind of covalent organic frame material and preparation method thereof and the application in fluorescent optical sensor
CN104478855B (en) 3-amino-4-((E)-pyridine-2(1-hydro)-alkenyl acetonitrile)-1,8-naphthalimide derivative
AU2011217066A1 (en) Indicator system for fibre optic sensor
WO2015058777A1 (en) Azatriangulenium salts as pet-quenched fluorescent probes
CN108587605B (en) Fe3+Molecular fluorescence compound and preparation method thereof
CA2892053A1 (en) Multi-layer device for selectively determining magnesium ion
JP3810260B2 (en) Method for determination of triaza-cryptands and alkali ions
CN108864046B (en) Fe2+Molecular fluorescence test fluid, preparation method and its application
CN106543226A (en) A kind of preparation and application for positioning mitochondrial ATP fluorescent probes
CN101672780B (en) Analytical method for detecting trace mercury in aqueous medium based on the color change of fluorescence
Yao et al. Metal-ion-mediated synergistic coordination: construction of AIE-metallogel sensor arrays for anions and amino acids
CN104151867A (en) Temperature and pH double-response cyclodextrin probe and preparation method thereof
CN101906049A (en) Fluorescent probe for detecting heparin content in blood as well as synthetic method and application
CN108801992B (en) Fe3+Molecular fluorescence sensor and preparation method thereof
CN108675989B (en) Fe3+Molecular fluorescence test agent and preparation method thereof
CN101659997B (en) Fluorescence detection method for distinguishing single stranded nucleotide from double stranded nucleotide
JP2006514680A (en) Solid-phase saccharide detection compound
CN111925316B (en) Two-photon fluorescence polar probe based on 4-fluorophenylethynyl and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant